CdTe thin films have been deposited using spray pyrolysis with and without electric field. The improvement in the film properties with the electric field is observed which is mainly due to the reduction of droplet size. The presence of CdTeO3 peaks in the X-ray diffraction pattern for films deposited without electric field at 350 °C is attributed to the slow dissociation of complexes containing Cd and Te ions on the substrate. The reduction in the droplet size under the influence of electric field and faster dissociation of droplets at high temperature leads to complete pyrolytic reaction for a nearly oxide free CdTe film formation. Energy dispersive X-ray analysis indicates stoichiometric Cd and Te atomic concentrations, with oxygen and chlorine impurities in varying amount for different substrate temperatures, with and without electric field. The presence of chlorine gives rise to an intense photoluminescence peak at 1.40 eV along with a weak peak at 0.84 eV. The intensities of both peaks diminish when the films are prepared with the electric field, due to reduction of chlorine concentration and morphological changes in the films.